CN107640775B - Method for preparing ZSM-5 molecular sieve by using solid waste - Google Patents
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Abstract
The invention relates to a method for preparing a ZSM-5 molecular sieve by using solid wastes, in particular to a preparation process for synthesizing the ZSM-5 molecular sieve by using the solid wastes such as rice hull ash, iron tailings, gold tailings and the like as raw materials to provide all or part of silicon sources and aluminum sources required by the synthesis of the ZSM-5 molecular sieve and simultaneously synthesizing the ZSM-5 molecular sieve without participation of a solvent and NaOH. Silicon source, aluminum source and Na2CO3∙10H2Mixing O, template agent or crystal seed, and crystallizing in reactor at constant temperature to obtain ZSM-5 molecular sieve2CO3∙10H2The O is applied to the process for synthesizing the ZSM-5 molecular sieve by taking solid waste as the raw material, and no secondary pollution is caused in the synthesis process. The method takes the rice hull ash, the iron tailings, the gold tailings and other solid wastes as raw materials to synthesize the ZSM-5 molecular sieve by a solvent-free method, has simple process and wide application range, can relieve the environmental problems caused by the solid wastes, and can realize high value-added utilization of the solid wastes.
Description
Technical Field
The invention belongs to the field of molecular sieve preparation and environmental protection. In particular to a method for preparing a ZSM-5 molecular sieve by using rice hull ash, iron tailings and gold tailings to provide all or part of silicon sources and aluminum sources required by the synthesis of the ZSM-5 molecular sieve and by using solid wastes, and simultaneously synthesizing the ZSM-5 molecular sieve containing hierarchical pores under the participation of no solvent and NaOH.
Background
Since the first report of the American Mobil company (USP3702886) in 1972, the ZSM-5 molecular sieve has been applied to a plurality of oil refining and chemical engineering processes due to the unique pore channel structure and shape-selective catalytic action, the preparation method is continuously improved, the preparation cost of the ZSM-5 molecular sieve is obviously reduced from the initial synthesis by adopting an organic amine template to the subsequent amine-free synthesis, and the application field of the ZSM-5 molecular sieve is continuously expanded by the technical progress of post-modification treatment and the like of the synthesized ZSM-5 molecular sieve product. For example, no ZSM-5 molecular sieve was used in the Fluid Catalytic Cracking (FCC) catalyst used in the oil refining industry at the early stage, and most of the current FCC catalysts added ZSM-5 molecular sieve to improve the catalyst performance and thus the product distribution. Since the FCC catalyst is a kind of catalyst with a large demand, the annual consumption of the FCC catalyst reaches several tens of thousands of tons in the chinese market, which results in an increase in demand for the ZSM-5 molecular sieve, and also requires a further reduction in the production cost of the ZSM-5 molecular sieve.
On the other hand, zeolite molecular sieves including ZSM-5 molecular sieves function as active components in FCC catalysts and the like, and good dispersion of the active components is important for the catalysts, so that the utilization efficiency of the active components can be improved. An important measure to improve the dispersion of the active components of the molecular sieve in the catalyst is to use molecular sieve products having as small a crystal size as possible. It is well known that nanocrystalline or mesoporous-introduced molecular sieves are essential for the manufacture of high performance catalysts because they can be optimized to provide additional potential in the fields of catalysis and adsorption applications due to the increase in surface area, reactive active sites and molecular diffusion. However, the size of the crystals of the molecular sieves synthesized by the existing solvent-free method is usually in the range of several micrometers, so that the synthesis of nanocrystalline molecular sieves by the solvent-free method is a great challenge.
The typical method of making ZSM-5 molecular sieves is by synthesis using an alkaline silica-alumina gel system. The system consists of sodium oxide, aluminum oxide, silicon oxide and water. The silicon source used for synthesizing the raw materials is generally sodium silicate, silica gel and the like, and the aluminum source is generally aluminum sulfate, sodium aluminate and the like. In the 20 th century and the 80 th century, quaternary ammonium salt or other organic amine is generally used as a template agent to synthesize the ZSM-5 molecular sieve (referred to as an amine method for short), and due to the fact that the price of the quaternary ammonium salt and other organic template agents is high, a technology (namely a seed crystal method or an amine-free method) for synthesizing the ZSM-5 molecular sieve by utilizing ZSM-5 molecular sieve seed crystals appears in the 20 th century and the 80 th century, and the preparation cost of the ZSM-5 molecular sieve is obviously reduced.
The synthesis process of the ZSM-5 molecular sieve basically adopts a hydrothermal method, a dry gel conversion method, a solvent-free method and the like. The hydrothermal synthesis system needs to contain a large amount of alkaline solution, and the raw materials need to be stirred, aged and the like before the synthesis process of the reaction kettle, so that the synthesis efficiency of the molecular sieve is reduced. The dry gel conversion method is a method for synthesizing a molecular sieve in a solid phase, comprises a gas phase conversion method and a steam auxiliary method, and needs to mix a silicon source, an aluminum source and water to prepare gel, and dry gel after water is removed is used for preparing the molecular sieve. The methods can not completely avoid the use of solvent in the process of preparing the ZSM-5 molecular sieve, generate a large amount of alkali-containing wastewater and reduce the space utilization rate of molecular sieve synthesis equipment. The solvent-free method is described inThe preparation process of the molecular sieve does not use any solvent, the prior solvent-free method mainly uses pure chemical reagents as raw materials, and the pure chemical reagents are directly placed into a reaction kettle to be sealed and kept stand for synthesis at a certain temperature after being simply mixed and ground4F、NH4Cl and other substances harmful to the environment are not suitable for industrial large-scale application, and no report of synthesizing the molecular sieve by using solid wastes as raw materials and using a solvent-free method is provided at present.
Disclosure of Invention
In order to solve the above problems, the main object of the present invention is to provide a method for synthesizing a solid waste material by mixing the raw materials using a solvent-free method and directly placing the mixture into a reaction kettle to seal and stand at a certain temperature, wherein the raw materials are free of NH4F、NH4Cl and other substances harmful to the environment, and the method for synthesizing the ZSM-5 molecular sieve with the nano-crystal hierarchical holes at low cost is green.
The raw materials comprise solid wastes such as rice hull ash, gold tailings and iron tailings, wherein the content of SiO2 in the rice hull ash reaches about 90%, the rice hull ash is amorphous, and the rice hull ash can be directly used as a silicon source to prepare the ZSM-5 molecular sieve; the iron tailings and the gold tailings in the raw materials mainly contain quartz, albite, potassium feldspar, anorthite, magnetite, pyrite, cordierite, talc and illite, and the gold tailings and the iron tailings are complex in components and contain various silicate minerals, magnetite impurities and pyrite impurities, and SiO2The content is more than 60 percent, and silicate minerals in the gold tailings and the iron tailings need to be activated.
The technical scheme of the invention is as follows: a method for preparing a ZSM-5 molecular sieve by using solid wastes specifically comprises the following steps:
step 1: mixing a silicon source, sodium carbonate decahydrate, an aluminum source substance and a template agent according to a certain proportion by taking solid waste as the silicon source, and mixing and grinding for 1-10 minutes;
step 2: and (3) placing the mixture obtained in the step (1) into a stainless steel reaction kettle, heating to 100-200 ℃, crystallizing for 3-96 hours, and after the crystallization is finished, rapidly cooling, washing and drying a filter cake to obtain the ZSM-5 molecular sieve containing the hierarchical pore structure.
Further, the silicon source, the sodium carbonate decahydrate, the aluminum source and the template agent are in the following proportion: n (TPABr)/n (SiO)2)＝0.1～2.0；n(Na2CO3·10H2O)/n(SiO2)＝0.1～10；n(SiO2)/n(Al2O3)＝20～+∞。
Further, the solid waste is rice hull ash, iron tailings or gold tailings, and when the iron tailings and the gold tailings are adopted, the iron tailings and the gold tailings need to be activated.
Further, the activation treatment process comprises the following steps: activating gold tailings and iron tailings by adopting an alkali sintering mode, wherein n (NaOH)/n (SiO)2) 1-4 ℃, the activation treatment temperature is 200-1000 ℃, and the activation treatment time is 1-10 hours. And mixing and stirring the activated alkali sintering product with water for 50-70 minutes, separating the product into a water-soluble substance and a water-insoluble solid, directly adjusting the pH value of the solution to 9 without solid-liquid separation, standing for 6-24 hours, and drying at the constant temperature of 80 ℃ to obtain solid powder.
Further, the iron tailings or gold tailings have the following components: the iron tailings or the gold tailings mainly contain quartz, albite, potash feldspar, anorthite, magnetite, pyrite, cordierite, talc and illite.
Furthermore, the iron tailings and the gold tailings are not subjected to acid leaching purification treatment before activation, so that acid-containing waste liquid is avoided.
The synthetic ZSM-5 molecular sieve and the preparation method thereof provided by the invention have the following characteristics:
(1) the raw material range of synthesizing the ZSM-5 molecular sieve by using the solvent-free method is expanded, new applications are found for solid wastes such as rice hull ash, iron tailings, gold tailings and the like, and the raw material cost for preparing the ZSM-5 molecular sieve is reduced.
(2) The ZSM-5 molecular sieve is prepared according to the method of the invention, and the raw materials of the reaction mixture do not contain solvent and sodium hydroxide. The method can improve the utilization rate of molecular sieve synthesis equipment, reduce the production cost of the molecular sieve and reduce the pollution in the production process of the molecular sieve.
(3) The ZSM-5 molecular sieve provided by the invention has high crystallinity and nano crystals, can shorten the diffusion path of reactant and product molecules in the molecular sieve crystals, and improves the catalytic production efficiency.
(4) Compared with the ZSM-5 molecular sieve synthesized by the traditional method, the ZSM-5 molecular sieve product prepared by the method contains a hierarchical pore structure.
Drawings
FIG. 1 is an X-ray diffraction (XRD) spectrum of a ZSM-5 molecular sieve synthesized from rice hull ash according to example 1 of the present invention.
FIG. 2 is a flow chart of a method for preparing a ZSM-5 molecular sieve by using solid wastes according to the present invention.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific embodiments.
The invention relates to a method for preparing a ZSM-5 molecular sieve by using solid wastes, which specifically comprises the following steps:
step 1: mixing a silicon source, sodium carbonate decahydrate, an aluminum source substance and a template agent according to a certain proportion by taking solid waste as the silicon source, and mixing and grinding for 1-10 minutes;
step 2: and (3) placing the mixture obtained in the step (1) into a stainless steel reaction kettle, heating to 100-200 ℃, crystallizing for 3-96 hours, and after the crystallization is finished, rapidly cooling, washing and drying a filter cake to obtain the ZSM-5 molecular sieve containing the hierarchical pore structure.
Further, the silicon source, the sodium carbonate decahydrate, the aluminum source and the template agent are in the following proportion: n (TPABr)/n (SiO)2)＝0.1～2.0；n(Na2CO3·10H2O)/n(SiO2)＝0.1～10；n(SiO2)/n(Al2O3)＝20～+∞。
Further, the solid waste is rice hull ash, iron tailings or gold tailings, and when the iron tailings and the gold tailings are adopted, the iron tailings and the gold tailings need to be activated.
Further, the activation treatment process comprises the following steps: activating gold tailings and iron tailings by adopting an alkali sintering mode, wherein N (N)aOH)/n(SiO2) 1-4 ℃, the activation treatment temperature is 200-1000 ℃, and the activation treatment time is 1-10 hours. And mixing and stirring the activated alkali sintering product with water for 50-70 minutes, separating the product into a water-soluble substance and a water-insoluble solid, directly adjusting the pH value of the solution to 9 without solid-liquid separation, standing for 6-24 hours, and drying at the constant temperature of 80 ℃ to obtain solid powder.
Further, the iron tailings or gold tailings have the following components: the iron tailings or the gold tailings mainly contain quartz, albite, potash feldspar, anorthite, magnetite, pyrite, cordierite, talc and illite, and the content of silicate in the iron tailings or the gold tailings is not lower than 50%.
Furthermore, the iron tailings and the gold tailings are not subjected to acid leaching purification treatment before activation, so that acid-containing waste liquid is avoided.
Furthermore, the ZSM-5 molecular sieve with the hierarchical pore structure can also be used as a seed crystal of the ZSM-5 molecular sieve.
Example 1:
taking 200-mesh rice hull ash as a raw material, taking 2g of rice hull ash, and sequentially adding 0.2g of sodium aluminate and 2.5g of Na2CO3·10H2O and 0.2g of TPABr are put in a mortar for grinding and mixing for 5 minutes, and the mixture is put in a sealed stainless steel reaction kettle to be heated to 100 ℃ and kept stand for crystallization for 72 hours at constant temperature. After crystallization, rapidly cooling, washing and drying the filter cake to obtain a crystallized product. Through X-ray diffraction (XRD) test, the product belongs to a ZSM-5 molecular sieve, the crystal size of the ZSM-5 molecular sieve is 40-200 nm, Fe and Mn impurities in the raw materials enter a molecular sieve framework, and the obtained ZSM-5 molecular sieve product contains micropores and mesopores. The XRD phase diagram is shown in figure 1.
Example 2:
using iron tailings as raw material, SiO2The content is 67%, 10g of iron tailings are taken to be activated for 3 hours in a muffle furnace at 500 ℃, the activated product is soaked in water for 1 hour, the pH of the filtrate is adjusted to 9, the filtrate is kept stand for 12 hours, and the powder obtained by drying is used as a raw material for synthesizing the ZSM-5 molecular sieve. 2g of filter residue, 0.2g of sodium aluminate and 2.5g of Na2CO3·10H2O and 0.2g TPABr were put in a mortar and ground for 5 minutes, and the mixture was put in a mortarHeating to 100 deg.c in a sealed stainless steel reactor, and standing for crystallization for 72 hr. After crystallization is finished, rapidly cooling, washing and drying a filter cake to obtain a crystallized product, wherein the crystal size of the ZSM-5 molecular sieve is 40-200 nm, Fe and Mn impurities in the raw materials enter a molecular sieve framework, and the obtained ZSM-5 molecular sieve product simultaneously contains micropores and mesopores. The XRD phase results are the same as in the first embodiment.
Example 3:
using iron tailings as raw material, SiO2The content is 67%, 10g of iron tailings are taken to be activated for 3 hours in a muffle furnace at 500 ℃, the activated product is soaked in water for 1 hour, the pH of the filtrate is adjusted to 9, the filtrate is kept stand for 12 hours, and the powder obtained by drying is used as a raw material for synthesizing the ZSM-5 molecular sieve. 2g of filter residue, 0.2g of sodium aluminate and 2.5g of Na2CO3·10H2And O and 0.2g of the ZSM-5 molecular sieve obtained in the first embodiment are placed in a mortar for grinding and mixing for 5 minutes, and the mixture is placed in a sealed stainless steel reaction kettle, heated to 100 ℃, kept at a constant temperature and crystallized for 72 hours. After crystallization is finished, rapidly cooling, washing and drying a filter cake to obtain a crystallized product, wherein the crystal size of the ZSM-5 molecular sieve is 40-200 nm, Fe and Mn impurities in the raw materials enter a molecular sieve framework, and the obtained ZSM-5 molecular sieve product simultaneously contains micropores and mesopores. The XRD phase results are the same as in the first embodiment.
Example 4:
using gold tailings as raw material, SiO2The content is 71%, 10g of iron tailings are taken to be activated for 3 hours in a muffle furnace at 500 ℃, the activated product is soaked in water for 1 hour, the pH of the filtrate is adjusted to 9, the filtrate is kept stand for 12 hours, and the powder obtained by drying is used as a ZSM-5 molecular sieve synthesis raw material. Filtering 3g of filter residue, 0.2g of sodium aluminate and 3g of Na2CO3·10H2O and 0.2g of TPABr are put into a mortar for grinding and mixing for 5 minutes, and the mixture is put into a sealed stainless steel reaction kettle to be heated to 100 ℃ and kept stand for crystallization for 72 hours at constant temperature. After crystallization is finished, rapidly cooling, washing and drying a filter cake to obtain a crystallized product, wherein the crystal size of the ZSM-5 molecular sieve is 40-200 nm, Fe and Mn impurities in the raw materials enter a molecular sieve framework, and the obtained ZSM-5 molecular sieve product simultaneously contains micropores and mesopores. The XRD phase results are the same as in the first embodiment.
Example 5:
using gold tailings as raw material, SiO2The content is 71%, 10g of iron tailings are taken to be activated for 3 hours in a muffle furnace at 500 ℃, the activated product is soaked in water for 1 hour, the pH of the filtrate is adjusted to 9, the filtrate is kept stand for 12 hours, and the powder obtained by drying is used as a ZSM-5 molecular sieve synthesis raw material. Filtering 3g of filter residue, 0.2g of sodium aluminate and 3g of Na2CO3·10H2And O and 0.2g of the ZSM-5 molecular sieve obtained in the first embodiment are placed in a mortar for grinding and mixing for 5 minutes, and the mixture is placed in a sealed stainless steel reaction kettle, heated to 100 ℃, kept at a constant temperature and crystallized for 72 hours. After crystallization is finished, rapidly cooling, washing and drying a filter cake to obtain a crystallized product, wherein the crystal size of the ZSM-5 molecular sieve is 40-200 nm, Fe and Mn impurities in the raw materials enter a molecular sieve framework, and the obtained ZSM-5 molecular sieve product simultaneously contains micropores and mesopores. The XRD phase results are the same as in the first embodiment.
Claims (5)
1. A method for preparing a ZSM-5 molecular sieve by using solid wastes specifically comprises the following steps:
step 1: mixing a silicon source, sodium carbonate decahydrate, an aluminum source substance and a template agent according to a certain proportion by taking solid waste as the silicon source, and mixing and grinding for 1-10 minutes; wherein the solid waste is rice hull ash, iron tailings or gold tailings; wherein the silicon source, the sodium carbonate decahydrate, the aluminum source and the template agent are in the following proportion: n (TPABr)/n (SiO)2)=0.1~2.0；n(Na2CO3∙10H2O)/n(SiO2)=0.1~10；n(SiO2)/n(Al2O3)=20~+∞；
Step 2: and (3) placing the mixture obtained in the step (1) into a stainless steel reaction kettle, heating to 100-200 ℃, crystallizing for 3-96 hours, and after the crystallization is finished, rapidly cooling, washing and drying a filter cake to obtain the ZSM-5 molecular sieve containing the hierarchical pore structure.
2. The method of claim 1, wherein when iron tailings and gold tailings are used as the silicon source, the iron tailings and the gold tailings are activated.
3. The method according to claim 2, wherein the activation treatment process is: activating gold tailings and iron tailings by adopting an alkali sintering mode, wherein n (NaOH)/n (SiO)2) 1-4, the activation treatment temperature is 200-1000 ℃, and the activation treatment time is 1-10 hours; and mixing and stirring the activated alkali sintering product with water for 50-70 minutes, separating the product into a water-soluble substance and a water-insoluble solid, directly adjusting the pH =9 of the solution without solid-liquid separation, standing for 6-24 hours, and drying at the constant temperature of 80 ℃ to obtain solid powder.
4. The process according to claim 2, wherein the iron or gold tailings have a composition: the iron tailings or the gold tailings mainly contain quartz, albite, potash feldspar, anorthite, magnetite, pyrite, cordierite, talc and illite.
5. The method according to claim 2, characterized in that the iron tailings and the gold tailings are not subjected to acid leaching purification treatment before activation, so that acid-containing waste liquid is avoided.
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| CN108190913B (en) * | 2018-03-02 | 2020-07-17 | 浙江大学 | Method for synthesizing silicon-rich ZSM-5 zeolite molecular sieve by adopting seed crystal guiding method |
| CN109081358A (en) * | 2018-08-13 | 2018-12-25 | 桂林理工大学 | A kind of method that non-ferrous metal tin ore tailing quickly prepares high-crystallinity ZSM-5 molecular sieve without acidleach removal of impurities |
| CN108910909B (en) * | 2018-09-30 | 2020-04-03 | 芜湖格丰环保科技研究院有限公司 | Method for preparing ZSM-5 molecular sieve by using laterite-nickel ore smelting waste residues |
| CN109876783B (en) * | 2019-04-04 | 2022-02-08 | 河北工业大学 | Method for preparing nano-bubble manganese silicate composite material by using iron tailings |
| CN110272058B (en) * | 2019-07-01 | 2022-08-09 | 中南大学 | MCM-41 ordered mesoporous material and preparation method thereof |
| CN110560152A (en) * | 2019-08-10 | 2019-12-13 | 桂林理工大学 | Method for directly preparing FeMn-ZSM-5 catalyst from tailings rich in iron and manganese |
| CN111847476A (en) * | 2020-06-30 | 2020-10-30 | 北京科技大学 | Preparation method of hierarchical pore ZSM-5 molecular sieve |
| CN113559920A (en) * | 2021-07-05 | 2021-10-29 | 青岛科技大学 | ZSM-5 molecular sieve/titanium dioxide composite material and preparation method thereof |
| CN115043414B (en) * | 2022-06-09 | 2023-12-29 | 青岛科技大学 | Hierarchical pore molecular sieve and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187462A (en) * | 1997-01-10 | 1998-07-15 | 中国石油化工总公司 | Process for synthesizing ZSM-5 molecular sieve |
| CN101723405A (en) * | 2008-10-24 | 2010-06-09 | 中国石油大学(北京) | Method for preparing ZSM-5 molecular sieves |
| CN104743573A (en) * | 2013-12-26 | 2015-07-01 | 中国科学院过程工程研究所 | ZSM-5 molecular sieve and preparation method thereof |
-
2017
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187462A (en) * | 1997-01-10 | 1998-07-15 | 中国石油化工总公司 | Process for synthesizing ZSM-5 molecular sieve |
| CN101723405A (en) * | 2008-10-24 | 2010-06-09 | 中国石油大学(北京) | Method for preparing ZSM-5 molecular sieves |
| CN104743573A (en) * | 2013-12-26 | 2015-07-01 | 中国科学院过程工程研究所 | ZSM-5 molecular sieve and preparation method thereof |
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